Non-fluoropolymer surface protection composition

ABSTRACT

The present invention encompasses a surface treatment composition which comprises a polyorganosiloxane fluid-silicone resin mixture and a carrier. The polyorganosiloxane fluid-silicone resin mixture comprises about 50% to about 99.99% by weight of one or more polyorganosiloxane fluid compounds, at least 0.01% by weight of one or more silicone resin, and a maximum of 5% by weight of water.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority to U.S. ProvisionalApplication Ser. No. 61/384,427, filed Sep. 20, 2010, which is hereinincorporated by reference.

FIELD OF THE INVENTION

The present invention relates to compositions that may be used toprotect surfaces from being stained. In particular, the compositions ofthe present invention are used to protect fabric from being stained.

BACKGROUND OF THE INVENTION

Numerous attempts have been made to develop a treatment composition thatprovides protection of surfaces by repelling water and oil based soilsfrom the surface. Fluoropolymers, such as those used in Scotchguard®from 3M, have become well established as stain repellant molecules.However, fluoropolymers are not preferred due to environmental, andhealth and safety concerns, such as potential and possibility ofpersistent bioaccumulation and toxicity.

The combination of polyorganosiloxane fluids and silicone resins inattempts to treat hard or soft surfaces are also known. See WO2007/065067, WO 2006/097207, WO 2006/097227, and EP 1057924 as examples.U.S. Patent Application Publication US 2006/0041026, by Mahr et al. ofWacker-Chemie GmbH, Munich, Germany discloses solvent based compositionscomprising polydimethylsiloxane fluids which deliver water-repellantbenefits on a wide range of substrates.

Unfortunately, to date, the attempts at non-fluoropolymer continue todemonstrate problems related to low efficiency, difficult to achieve thedesired benefits at affordable cost and preferred format; challenging toobtain stable products without significant sacrifices on other desiredcharacteristics of the products. A continued need exists for anon-fluoropolymer technology that delivers significant water and oilysoil repellency to obtain a stain prevention benefit with highefficiency in a convenient form.

SUMMARY OF THE INVENTION

The present invention encompasses a surface treatment composition whichcomprises a polyorganosiloxane fluid-silicone resin mixture and acarrier. The polyorganosiloxane fluid-silicone resin mixture comprisesfrom about 50% to about 99.9%, by weight of the mixture, of one or morepolyorganosiloxane fluid compounds; at least 0.01%, by weight of themixture, of one or more silicone resins; and a maximum of about 5%, byweight of the mixture, of water.

Each of the one or more polyorganosiloxane fluid compounds contains atleast 80 mol % of units selected from the group consisting of units ofthe general formulae Ia, Ib, II and III:

R¹ ₂SiO_((2/2))  (Ia),

R¹ _(a)R² _(b)SiO_((2/2))  (Ib),

R³ ₃SiO_((1/2))  (II),

R³ ₂R⁴SiO_((1/2))  (III),

in which a has the value 0, 1 or 2, b has the value 1 or 2, and the sumof a and b is equal to 2. R¹ means monovalent hydrocarbon residues with1 to 40 carbon atoms, optionally substituted with halogens. R² meanseither a) aminoalkyl residues of the general formula IV:

—R⁵—NR⁶R⁷  (IV),

wherein R⁵ means divalent hydrocarbon residues with 1 to 40 carbonatoms, R⁶ means monovalent hydrocarbon residues with 1 to 40 carbonatoms, H, hydroxymethyl or alkanoyl residues, and R⁷ means a residue ofthe general formula V

—(R⁸—NR⁶)_(x)R⁶  (V),

wherein x has the value 0 or an integer value from 1 to 40, and R⁸ meansa divalent residue of the general formula VI

—(CR⁹ ₂—)_(y)—  (VI),

wherein y has an integer value from 1 to 6, and R⁹ means H or monovalenthydrocarbon residues with 1 to 40 carbon atoms, or b) aminoalkylresidues of the general formula IV wherein R⁶ and R⁷ together with the Natom forms a cyclic organic residue with 3 to 8 —CH₂— units, and wherenonadjacent —CH₂— units can be replaced by units that are chosen from—C(═O)—, —NH—, —O—, and —S—. R³ means monovalent hydrocarbon residueswith 1 to 40 carbon atoms optionally substituted with halogens. R⁴ meansthe residues —OR or —OH, wherein R means monovalent hydrocarbon residueswith 1 to 40 carbon atoms, optionally substituted with halogens.Additionally, the average ratio of the sum of the units of formulae Iaand Ib to the sum of units of formulae II and III within the one or morepolyorganosiloxane fluid compounds ranges from about 0.5 to about 500.The average ratio of units of formula II to the units of formula IIIwithin the one or more polyorganosiloxane fluid compounds ranges fromabout 1.86 to about 100. The one or more polyorganosiloxane fluidcompound have an average amine number of at least about 0.01 meq/g ofpolyorganosiloxane fluid compounds.

Each of the one or more silicone resins of thepolyorganosiloxane-silicone resin mixture contains at least about 80 mol% of units selected from the group consisting of units of the generalformulas VII, VIII, IX and X:

R¹⁰ ₃SiO_(1/2)  (VII),

R¹⁰ ₂SiO_(2/2)  (VIII),

R¹⁰SiO_(3/2)  (IX),

SiO_(4/2)  (X),

in which R¹⁰ means H, —OR or —OH residues or monovalent hydrocarbonresidues with 1 to 40 carbon atoms, optionally substituted withhalogens, at least 20 mol % of the units are selected from the groupconsisting of units of the general formulas IX and X, and a maximum of10 wt % of the R¹⁰ residues are —OR and —OH residues.

DETAILED DESCRIPTION OF THE INVENTION Surface Treatment Composition

The present invention relates to compositions to be used for thetreatment of surfaces. Certain embodiments of the compositions providewater and/or oil repellency to the treated surface thereby reducing thepropensity of the treated surface to become stained by deposited wateror oil based soils.

By “surfaces” it is meant any inanimate surface. These surfaces mayinclude porous or non-porous, absorptive or non-absorptive substrates.Surfaces may include, but are not limited to, celluloses, paper, naturaland/or synthetic textiles fibers and fabrics, imitation leather andleather. Selected embodiments of the present invention are applied tonatural and/or synthetic textile fibers and fabrics.

By “treating a surface” it is meant the application of the compositiononto the surface. The application may be performed directly, such as thespray or wiping the composition onto a hard surface. The composition mayor may not be rinsed off depending on the desired benefit.

The present invention also encompasses the treatment of a fabric as thesurface. This can be done either in a “pretreatment mode”, where thecomposition is applied neat onto the fabric before the fabrics arewashed or rinsed, or a “post-treatment mode”, where the composition isapplied neat onto the fabric after the fabric is washed or rinsed. Thetreatment may be performed in a “soaking mode”, where the fabric isimmersed and soaked in a bath of neat or diluted composition. Thetreatment may also be performed in a “through the wash” or “through therinse” mode where the treatment composition, as defined herein, is addedto the wash cycle or the rinse cycle of a typical laundry wash machinecycle. When used in the wash or rinse cycle, the compositions aretypically used in a diluted form. By “diluted form” it is meant that thecompositions may be diluted in the use, preferably with water at a ratioof water to composition up to 500:1, or from 5:1 to 200:1, or from 10:1to 80:1.

Polyorganosiloxane-Silicone Resin Mixture

The present invention encompasses a surface treatment composition whichcomprises a polyorganosiloxane-silicone resin mixture and a carrier. Thepolyorganosiloxane-silicone resin mixture comprises between about 50% toabout 99.9% by weight of the mixture, of one or more polyorganosiloxanefluid compounds, at least about 0.01% by weight of the mixture, of oneor more silicone resins, and a maximum of about 5% by weight of themixture, of water. Certain embodiments of thepolyorganosiloxane-silicone resin mixture may comprise between about 75%to about 98% of the polyorganosiloxane fluid compounds. Otherembodiments may comprise between about 80% to about 90%, oralternatively between about 80% to about 87% of the polyorganosiloxanefluid compounds. Additionally, certain embodiments of thepolyorganosiloxane-silicone resin mixture may comprise between about0.1% and 50%, or between about 2% and about 30% of the silicone resins.Other embodiments of the mixture may comprise between about 5% and about20% of the silicone resins.

Each of the one or more polyorganosiloxane fluid compounds contains atleast 80 mol % of units selected from the group consisting of units ofthe general formulae Ia, Ib, II and III:

R¹ ₂SiO_((2/2))  (Ia),

R¹ _(a)R² _(b)SiO_((2/2))  (Ib),

R³ ₃SiO_((1/2))  (II),

R³ ₂R⁴SiO_((1/2))  (III),

in which a has the value 0, 1 or 2, b has the value 1 or 2, and the sumof a and b is equal to 2. R¹ means monovalent hydrocarbon residues with1 to 40 carbon atoms, optionally substituted with halogens. R² meanseither a) aminoalkyl residues of the general formula IV:

—R⁵—NR⁶R⁷  (IV),

wherein R⁵ means divalent hydrocarbon residues with 1 to 40 carbonatoms, R⁶ means monovalent hydrocarbon residues with 1 to 40 carbonatoms, H, hydroxymethyl or alkanoyl residues, and R⁷ means a residue ofthe general formula V

—(R⁸—NR⁶)_(x)R⁶  (V),

wherein x has the value 0 or an integer value from 1 to 40, and R⁸ meansa divalent residue of the general formula VI

—(CR⁹ ₂—)_(y)—  (VI),

wherein y has an integer value from 1 to 6, and R⁹ means H or monovalenthydrocarbon residues with 1 to 40 carbon atoms, or b) aminoalkylresidues of the general formula IV wherein R⁶ and R⁷ together with the Natom forms a cyclic organic residue with 3 to 8 —CH₂— units, and wherenonadjacent —CH₂— units can be replaced by units that are chosen from—C(═O)—, —NH—, —O—, and —S—. R³ means monovalent hydrocarbon residueswith 1 to 40 carbon atoms optionally substituted with halogens. R⁴ meansthe residues —OR or —OH, wherein R means monovalent hydrocarbon residueswith 1 to 40 carbon atoms, optionally substituted with halogens.

Additionally, the average ratio of the sum of units of formulae Ia andIb to the sum of units of formulae II and III within the one or morepolyorganosiloxane fluid compounds may range from about 0.5 to about500. The average ratio of units of formula II to the units of formulaIII within the one or more polyorganosiloxane fluid compounds may rangefrom about 1.86 to about 100. The one or more polyorganosiloxane fluidcompounds have an average amine number of at least about 0.01 meq/g ofpolyorganosiloxane fluid compounds.

The monovalent hydrocarbon residues R, R¹, R³, R⁶, R⁹ and R¹⁰ can behalogen-substituted, linear, cyclic, branched, aromatic, saturated orunsaturated. Some embodiments of the monovalent hydrocarbon residues R,R¹, R³, R⁶, R⁹ and R¹⁰ have from 1 to 6 carbon atoms, including alkylresidues and phenyl residues. Certain embodiments have halogensubstituents such as fluorine and/or chlorine. Monovalent hydrocarbonresidues R, R¹, R³, R⁶, R⁹ and R¹⁰ methyl, ethyl and phenyl are usefulin the present compositions.

The divalent hydrocarbon residues R⁵ can be halogen substituted, linear,cyclic, branched, aromatic, saturated or unsaturated. The residues R⁵may have from 1 to 10 carbon atoms. Alkylene residues with 1 to 6 carbonatoms, including propylene, are especially useful embodiments. If R⁵ ishalogenated, the halogen substituents may be fluorine and chlorine.

Residues R⁶ may be alkyl and/or alkanoyl residues. Embodiments of R⁶ maycontain halogen substituents such as fluorine and chlorine. Embodimentsof R⁶ which are alkanoyl residues may have the general formula—C(═O)OR¹¹, where R¹¹ has the meanings and preferred meanings of R¹described above. Especially preferred substituents R⁶ are methyl, ethyl,cyclohexyl, acetyl and hydrogen.

Cyclic organic residues may be formed from the connection of R⁶ and R⁷in the general formula IV together with the bonded N atom. These cyclicresidues include pentacycles and hexacycles, such as the residues ofpyrrolidine, pyrrolidin-2-one, pyrrolidin-2,4-dione, pyrrolidin-3-one,pyrazol-3-one, oxazolidine, oxazolidin-2-one, thiazolidine,thiazolidin-2-one, piperidine, piperazine, piperazin-2,5-dione andmorpholine.

Embodiments of the residues R² include —CH₂NR⁶R⁷, —(CH₂)₃NR⁶R⁷,—(CH₂)₃N(R⁶), and —(CH₂)₂N(R⁶)₂. Examples include theaminoethylaminopropyl and cyclohexylaminopropyl residues.

In certain embodiments of the polyorganosiloxane fluid b has the value 1or 2. Some embodiments have the sum of a+b having an average value offrom about 1.9 to about 2.2.

In some useful embodiments the ratio of a to b is chosen so that thepolyorganosiloxane fluid compounds have an amine number of at leastabout 0.1, and some at least 0.3, meq/g polyorganosiloxane fluidcompound. The amine number designates the number of milliliters of 1Nhydrochloric acid which are required for neutralizing 1 gram ofpolyorganosiloxane fluid. Some embodiments have the amine number of thepolyorganosiloxane fluid is being a maximum of about 7. Others have amaximum of about 2.0, and yet others have a maximum of 1.0 meq/gpolyorganosiloxane fluid. x may have the value of 0 or a value from 1 to18. Certain embodiments have x being from 1 to 6. Certain embodiments ofthe fluid have y having a value of 1, 2 or 3. The polydimethylsiloxanefluids contain at least 3, especially at least 10 units of the generalformula I.

The viscosity of the polyorganosiloxane fluid compounds is at leastabout 1 mPa·s at 25° C., especially at least about 10 mPa·s, and has amaximum of about 100,000, especially at least about 10,000 mPa·s,Certain embodiments of the polyorganosiloxane fluid compound have aviscosity of at least about 100 mPa·s and a maximum of 5,000 mPa·s, at25° C.

The average ratio of the units of the general formula I to the sum ofunits II and III may range from about 0.5 to about 500. In certainembodiments the ratio may be at least about 10, particularly at leastabout 50 and range to a maximum of about 250, particularly a maximum ofabout 150.

The ratio of the units II to units III may range from about 1.86 toabout 100. Useful embodiments may have this ratio being at least about 3and may range to a maximum of about 70. Other embodiments may have thisration being at least about 6 or at least about 10, and may range to amaximum of about 50.

Each of the one or more silicone resins of thepolyorganosiloxane-silicone resin mixture contains at least 80 mol % ofunits selected from the group consisting of units of the generalformulas VII, VIII, IX and X

R¹⁰ ₃SiO_(1/2)  (VII),

R¹⁰ ₂SiO_(2/2)  (VIII),

R¹⁰SiO_(3/2)  (IX),

SiO_(4/2)  (X),

in which R¹⁰ means H, —OR or —OH residues or monovalent hydrocarbonresidues with 1 to 40 carbon atoms, optionally substituted withhalogens. Certain useful embodiments of the polyorganosiloxane-siliconeresin mixture may comprise silicone resins comprising at least about90%, at least about 95%, or at least about 98% of units selected fromthe group consisting of units of the general formulas VII, VIII, IX andX.

The silicone resins are preferably MQ silicone resins (MQ) comprising atleast 80 mol % of units, preferably at least 95 mol % and particularlyat least 97 mol % of units of the general formulae VII and X. Theaverage ratio of units of the general formulae VII to X is preferably atleast 0.25, particularly at least 0.5 and preferably 4, more preferablyat most 1.5.

The silicone resins (S) are also preferably DT silicone resins (DT)comprising at least 80 mol % of units, preferably at least 95 mol % andparticularly at least 97 mol % of units of the general formulae VIII andIX. The average ratio of units of the general formulae VIII to IX ispreferably at least 0.01, particularly at least 0.02 and preferably atmost 3.5, more preferably at most particularly at most 0.5.

At least 20 mol % of the units of the silicone resins are selected fromthe group consisting of units of the general formulas IX and X. Otherembodiments comprise silicone resins have at least 40% or even 50% ofunits selected from the group consisting of units of the generalformulas IX and X, A maximum of 10 wt % of the R¹⁰ residues in the oneor more silicone resins are —OR and —OH residues. In other usefulembodiments a maximum of 3% or even 1% may be desired.

The carrier of the surface treatment composition may be any knownmaterial, generally, but not necessarily, a liquid useful in deliveringthe polyorganosiloxane-silicone resin mixture to the surface which isdesired to be treated. The carrier may be as simple as a singlecomponent delivery vehicle such as water or alcohol which would allowthe mixture to be sprayed onto a surface. Alternatively, the carrier maybe complex such as a cleaning composition such as a laundry detergentwhere the mixture would be applied in conjunction with the otherbeneficial uses of the complex carrier.

Optional Adjunct Ingredients

To enhance the performance of the surface treatment composition of thepresent invention, additional deposition aid polymers may be added. Asused herein, “deposition aid polymer” refers to any polymer orcombination of polymers that enhance the deposition of fabric careagent(s) onto fabric during laundering. Without wishing to be bound bytheory, it is believed that in order to drive the fabric care agent ontothe fabric, the net charge of the deposition polymer is positive inorder to overcome the repulsion between the fabric care agent and thefabric since most fabrics are comprised of fabric fibers that have aslightly negative charge in aqueous environments. Examples of fibersexhibiting a slightly negative charge in water include but are notlimited to cotton, rayon, silk, wool, and the like.

The deposition aid of the present disclosure may be a cationic oramphoteric oligomer or polymer or a combination or blend of cationicand/or amphoteric oligomers and/or polymers that enhance the depositionof the fabric care composition onto the surface of the fabric or fiberduring the treatment process. Without wishing to be bound by any theory,it is believed that in order to drive the fabric care agent onto thesurface of the fabric, the net charge of the deposition aid, such as apositive net charge, may be used to overcome repulsive interactionsbetween the fabric care agent and the fabric surface. For example, manyfabrics (such as cotton, rayon, silk, wool, etc.) are comprised offibers that may have a slightly negative charge in aqueous environment.In certain embodiments, an effective amphoteric or cationicoligomeric/polymeric deposition aid may be characterized by a strongbinding capability with the present fabric care agents and compositionsvia physical forces, such as, van der Waals forces, and/or non-covalentchemical binds such as hydrogen bonding and/or ionic bonding. In someembodiments, the deposition aids may also have a strong affinity tonatural fabric fibers, such as cotton or wool fibers.

In particular embodiments, the deposition aids described herein arewater soluble and may have flexible molecular structures such that theymay associate with the surface of a fabric care agent particle or holdseveral of the particles together. Therefore, the deposition enhancingagent may typically not be cross-linked and typically does not have anetwork structure.

According to certain embodiments of the fabric care compositions of thepresent disclosure, the amphoteric or cationic oligomeric/polymericdeposition aid may be a cationic polymer selected from the groupconsisting of a cationic polysaccharide, a cationic guar, a cationiclignin, a cationic polymer, an amine containing polymer, an amidecontaining polymer, and combinations of any thereof. The term “cationicpolymer” refers to a polymer having a net cationic charge. Polymerscontaining amine groups or other protonatable groups are included in theterm “cationic polymer,” wherein the polymer is protonated at the pH ofintended use. In specific embodiments, the cationic polymer may be abranched cationic polymer. For example, according to certainembodiments, the cationic polymer may be a branched cationicpolysaccharide, wherein the polysaccharide has a fraction ofalpha-1,4-glycosidic linkages of at least about 0.01 up to about 1.0.

In another aspect, the fabric care composition and/or treatmentcomposition may comprise a deposition aid selected from the groupconsisting of cationic or amphoteric polysaccharides. Suitable cationicpolysaccharides for the various embodiments of the deposition aidsdescribed herein include, but are not limited to, cationic cellulosederivatives, cationic and amphoteric cellulose ethers, cationic oramphoteric galactomannan, cationic guar gum derivatives, cationic oramphoteric starches and derivatives, and cationic chitosan andderivatives. In specific embodiments, the branched cationicpolysaccharides may be a branched cationic starch.

In some embodiments, the cationic polysaccharide deposition aid may be acationic guar derivative having a general formula (A):

where G is a galactomannan backbone; R¹³ is a group selected from CH₃,CH₂CH₃, phenyl, a C₈-C₂₄ alkyl group (linear or branched) andcombinations thereof; R¹⁴ and R¹⁵ are groups independently selected fromCH₃, CH₂CH₃, phenyl, and combinations thereof; and Z⁻ is a suitableanion. In certain embodiments, the guar derivatives include guarhydroxypropyl trimethyl ammonium chloride. Examples of cationic guargums are Jaguar™ C13 and Jaguar™ Excel, available from Rhodia, Inc.(Cranberry, N.J.).

In one aspect, the fabric care and/or treatment composition may comprisefrom about 0.01% to about 10%, or from about 0.05 to about 5%, or fromabout 0.1 to about 3% of the deposition aid. Suitable deposition aidsare disclosed in, for example, U.S. application Ser. No. 12/080,358.

In one aspect, the one or more deposition aids may be a cationicpolymer. In one aspect, the deposition aid may comprise a cationicpolymer having a cationic charge density of from about 0.1 meq/g toabout 23 meq/g from about 0.1 to about 12 meq/g, or from about 0.3 toabout 7 meq/g, at the pH of intended use of the composition. Foramine-containing polymers, wherein the charge density depends on the pHof the composition, charge density is measured at the pH of the intendeduse of the product. Such pH will generally range from about 2 to about11, more generally from about 2.5 to about 9.5. Charge density iscalculated by dividing the number of net charges per repeating unit bythe molecular weight of the repeating unit. The positive charges may belocated on the backbone of the polymers and/or the side chains ofpolymers. For example, for the copolymer of acrylamide anddiallyldimethylammonium chloride with a monomer feed ratio of 70:30, thecharge density of the feed monomers is about 3.05 meq/g. However, ifonly 50% of diallyldimethylammonium is polymerized, the polymer chargedensity is only about 1.6 meq/g. The polymer charge density may bemeasured by dialyzing the polymer with a dialysis membrane or by NMR.For polymers with amine monomers, the charge density depends on the pHof the carrier. For these polymers, charge density is measured at a pHof 7.

In one aspect, the cleaning and/or treatment composition may comprise anamphoteric deposition aid polymer so long as the polymer possesses a netpositive charge. The polymer may have a cationic charge density of fromabout 0.05 meq/g to about 12 meq/g.

Suitable polymers may be selected from the group consisting of cationicor amphoteric polysaccharides, polyethylene imine and its derivatives,and a synthetic polymer made by polymerizing one or more cationicmonomers selected from the group consisting of N,N-dialkylaminoalkylacrylate, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylamino alkylacrylamide, N,N-dialkylaminoalkylmethacrylamide, quaternized N,Ndialkylamino alkyl acrylate, quaternized N,N-dialkylaminoalkylmethacrylate, quaternized N,N-dialkylaminoalkyl acrylamide, quaternizedN,N-dialkylaminoalkylmethacrylamide,methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammoniumdichloride,N,N,N,N′,N′,N″,N″-heptamethyl-N″-3-(1-oxo-2-methyl-2-propenyl)aminopropyl-9-oxo-8-azo-decane-1,4,10-triammoniumtrichloride, vinylamine and its derivatives, allylamine and itsderivatives, vinyl imidazole, quaternized vinyl imidazole and diallyldialkyl ammonium chloride and combinations thereof, and optionally asecond monomer selected from the group consisting of acrylamide,N,N-dialkyl acrylamide, methacrylamide, N,N-dialkyl methacrylamide,C₁-C₁₂ alkyl acrylate, C₁-C₁₂ hydroxyalkyl acrylate, polyalkylene glyolacrylate, C₁-C₁₂ alkyl methacrylate, C₁-C₁₂ hydroxyalkyl methacrylate,polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinylformamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinylpyrrolidone, vinyl imidazole, vinyl caprolactam, and derivatives,acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid,styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) andtheir salts. The polymer may optionally be branched or cross-linked byusing branching and crosslinking monomers. Branching and crosslinkingmonomers include ethylene glycoldiacrylate divinylbenzene, andbutadiene. A suitable polyethyleneinine useful herein is that sold underthe trade name Lupasol® by BASF, AG, Lugwigshafen, Germany

In another aspect, the deposition aid may be selected from the groupconsisting of cationic polysaccharides, cationic hydroxy ethyl cellulose(such as Cat HEC polymer PK having a molecular weight of about 400,000Daltons and a charge density of 1.25 meq/g, commercially available fromDow Chemical, Midland Mich.), cationic starches (such as Akzo, EXP5617-2301-28 (National Starch 126290-82), available from NationalStarch, Bridgewater, N.J.), polyethylene imine and its derivatives,poly(acrylamide-co-diallyldimethylammonium chloride),poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride),poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternizedderivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate)and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethylaminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethylaminoethyl methacrylate), poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride),poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid),poly(acrylamide-methacrylamido propyltrimethyl ammoniumchloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride) (suchas that sold under trade names: Merquat® 100 and having a molecularweight of 150,000 Daltons, commercially available from Nalco Co.,Naperville, Ill.), poly(vinylpyrrolidone-co-dimethylaminoethylmethacrylate), poly(ethyl methacrylate-co-quaternized dimethylaminoethylmethacrylate), poly(ethyl methacrylate-co-oleylmethacrylate-co-diethylaminoethyl methacrylate),poly(diallyldimethylammonium chloride-co-acrylic acid), poly(vinylpyrrolidone-co-quaternized vinyl imidazole) andpoly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammoniumdichloride). In a specific embodiment, the deposition aid may be aterpolymer with a mole ratio of 90% polyacrylamide:5% acrylic acid:5%methylenebis-acrylamide-methacrylamido-propyl trimethylammonium chloride(“MAPTAC”, sold under the trade names TX12528SQ, or Merquat® 5300,commercially available from Nalco Co, Naperville, Ill.). Suitabledeposition aids include Polyquaternium-1, Polyquaternium-5,Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-11,Polyquaternium-14, Polyquaternium-22, Polyquaternium-28,Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as namedunder the International Nomenclature for Cosmetic Ingredients.

In one aspect, the deposition aid may comprise polyethyleneimine or apolyethyleneimine derivative. In another aspect, the deposition aid maycomprise a cationic acrylic based polymer. In another aspect, thedeposition aid may comprise a cationic polyacrylamide. In anotheraspect, the deposition aid may comprise a polymer comprisingpolyacrylamide and polymethacrylamidoproply trimethylammonium cation. Inanother aspect, the deposition aid may comprisepoly(acrylamide-N,N-dimethylaminoethyl acrylate) and its quaternizedderivatives. In this aspect, the deposition aid may be that sold underthe trade name Sedipur®, available from BTC Specialty Chemicals, a BASFGroup, Florham Park, N.J. In another aspect, the deposition aid maycomprise poly(acrylamide-co-methacrylamidopropyltrimethyl ammoniumchloride). In another aspect, the deposition aid may be a non-acrylamidebased polymer, such as that sold under the trade name Rheovis® CDE,available from Ciba Specialty Chemicals, a BASF group, Florham Park,N.J., or as disclosed in U.S. Published Application No. 2006/0252668.

Another group of suitable cationic polymers may includealkylamine-epichlorohydrin polymers which are reaction products ofamines and oligoamines with epicholorohydrin, for example, thosepolymers listed in, for example, U.S. Pat. Nos. 6,642,200 and 6,551,986.Examples include dimethylamine-epichlorohydrin-ethylenediamine,available under the trade name Cartafix® CB and Cartafix® TSF fromClariant, Basel, Switzerland.

Another group of suitable synthetic cationic polymers may includepolyamidoamine-epichlorohydrin (PAE) resins of polyalkylenepolyaminewith polycarboxylic acid. The common PAE resins may include thecondensation products of diethylenetriamine with adipic acid followed bya subsequent reaction with epichlorohydrin. Suitable examples areavailable from Hercules Inc. of Wilmington Del. under the trade nameKymene™ or from BASF AG (Ludwigshafen, Germany) under the trade nameLuresin™. These polymers are described in “Wet Strength Resins and theirApplications,” edited by L. L. Chan, TAPPI Press (1994).

In various embodiments, the weight-average molecular weight of theoligomeric/polymeric deposition aids may range from about 500 to about10,000,000, from about 1,000 to about 5,000,000, or from about 10,000 toabout 5,000,000 Daltons, as determined by size exclusion chromatographyrelative to polyethyleneoxide standards with RI detection. In oneaspect, the MW of the cationic polymer may be from about 50,000 to about3,000,000 Daltons.

The cationic polymers may contain charge neutralizing anions such thatthe overall polymer is neutral under ambient conditions. Non-limitingexamples of suitable counter ions (in addition to anionic speciesgenerated during use) include chloride, bromide, sulfate, methylsulfate,sulfonate, methylsulfonate, carbonate, bicarbonate, formate, acetate,citrate, nitrate, and mixtures thereof.

Useful cationic polysaccharides, such as the branched cationicpolysaccharides, such as the branched cationic starches, describedherein may have at least one of a viscosity of less than about 1000centipoise (cps), a charge density ranging from about 0.001milliequivalents per gram (meq/g) of the polymer to about 5.0 meq/g ofthe polymer, and a weight average molecular weight ranging from about500 Daltons to about 10,000,000 Daltons. In one embodiment, thedeposition aid may be a cationic starch (such as Akzo, EXP 5617-2301-28(National Starch 126290-82), available from National Starch,Bridgewater, N.J.) having a structure (XI):

where R¹⁶ may be —OH or —(O)_(p)—(CH₂)_(n)(CH(OH))_(m)CH₂N⁺(CH₃)₃ wherep is 0 or 1, n is 1-10 and m is 0 or 1, provided that at least one R¹⁶group per substituted glucose unit is not —OH, and having a suitablecounteranion, charge density of from about 0.35 to about 0.6 meq/g, anamylose content of about 28%, a water fluidity (WF) of from about 62 toabout 70, and a molecular weight of from about 1,200,000 Daltons toabout 3,000,000 Daltons. In one specific embodiment, the starch may bederived from maize, and modified with R¹⁶ where—O—CH₂CH(OH)_(m)CH₂N⁺(CH₃)₃, and the charge density may be about 0.42meq/g, the molecular weight may be about 1,500,000 Daltons, and theamylose content may be about 28%.

As used herein, the charge density of the cationic or amphotericpolymers means the measurement of the charge of a polymer (measured inmeq) per gram of the polymer and may be calculated, for example, bydividing the number of net charges per repeating unit by the molecularweight of the repeating unit. As recited above, in one embodiment, thecharge density of the deposition aid may range from about 0.001 meq/g toabout 5.0 meq/g of polymer. In another embodiment, the charge density ofthe deposition aid may range from about 0.1 meq/g to about 3.0 meq/g ofpolymer. According to the various embodiments, the charges, for example,the positive charges may be located on the backbone of the polymerand/or on a side chain of the polymer.

Other embodiments of the branched cationic polysaccharides may have aweight average molecular weight ranging from about 50,000 Daltons toabout 10,000,000 Daltons, or even from about 100,000 Daltons to about5,000,000 Daltons. Certain embodiments of branched cationic celluloses(including cationic hydroxyethyl cellulose) may have a weight averagemolecular weight ranging from about 200,000 Daltons to about 3,000,000Daltons and certain embodiments of the cationic guars may have a weightaverage molecular weight ranging from about 500,000 Daltons to about2,000,000 Daltons.

Other branched cationic polymers can include branched cationic ligninsand branched cationic synthetic polymers. Branched cationic ligninsinclude lignin structures, such as, but not limited to ligninsulfonates, Kraft lignins, soda lignins, organosolv lignins, softwoodlignin, hardwood lignin, steam explosion lignins, cellulosic grasseslignins, corn stover lignins, and combinations of any thereof, that havebeen modified to have cationic substituents, such as quaternary ammoniumcontaining substituents. Modifying the lignin polymer may include, forexample, substituting one or more of the hydroxyl groups on a ligninpolymer backbone with one or more R substituent groups having a cationiccharge, such as a quaternary ammonium charged group. In otherembodiments, modifying the lignin polymer may include substituting atleast one of the hydroxy, methoxy or aromatic carbons on the ligninpolymer backbone with at least one R substituent group having a cationiccharge.

The synthetic cationic or amphoteric oligomeric/polymeric depositionaids may be random, block or grafted copolymers and may be linear orbranched. Certain embodiments of the synthetic oligomeric/polymericdeposition aid may have a weight average molecular weight ranging fromabout 2,000 Daltons to about 10,000,000 Daltons, or in specificembodiments from about 10,000, Daltons to about 3,000,000 Daltons oreven ranging from about 500,000 Daltons to about 2,000,000 Daltons.

Specific embodiments of the fabric care compositions described hereinmay further comprise a surfactant quencher. Without intending to belimited by any theory, it is believed that certain surfactants mayinhibit suitable and uniform deposition of at least one of thehydrophobic fluid and/or the particulate material onto the fabric orfiber surface. Therefore, excess or unintended surfactant in thecomposition or wash/rinse solution may be quenched or otherwise removedusing the surfactant quencher. According to certain embodiments, thesurfactant quencher may be present in from about 0.001% to about 5.0% byweight of the fabric care composition, or in other embodiments fromabout 0.05% to about 3.0%. The surfactant quencher according to variousembodiments may have a solubility in the wash solution ranging fromabout 0.1% to about 40%. In other embodiments, the surfactant quenchermay be a cationic surfactant quencher having a cationic charge rangingfrom about 0.1 milliequivalents/gram (meq/g) to about 23 meq/g. Infurther embodiments the surfactant quencher may have a molecular weightranging from about 50 g/mole to about 1000 g/mole. In particularembodiments, the surfactant quencher may be coconut trimethyl ammoniumchloride, dimethyl hydroxymethyl lauryl ammonium chloride, STEPANQUAT®6585 (dipalmethyl hydroxyethylammonium methosulfate, lauryl trimethylammonium chloride or ditallow dimethyl ammonium chloride (“DTDMAC”)and/or other cationic surfactants, including blends of the varioussurfactant quenchers.

Further embodiments of the fabric care compositions described herein mayfurther comprise a dispersant. As used herein, a dispersant is achemical compound or compounds that are used to stabilize an emulsion,dispersion or suspension of particles in a liquid. Suitable dispersantsfor use in the various embodiments described herein include non-ionicsurfactants, polymeric surfactants, and silicone based dispersants.According to various embodiments, the dispersant may comprise from about0.001% to 5% by weight of the composition; in certain embodiments from0.05% to 2% by weight of the composition and in specific embodimentsfrom 0.05%-0.5% by weight of the composition.

For example, suitable non-ionic surfactant include, but are not limitedto, ethoxylated alcohols (aliphatic ethoxylate), polyethylene oxide(PEO) caprilic acid, PEO stearic acid, PEO oleic acid, PEO Lauric acid,nonionic hydroxylamines, ethoxylated alkylphenols, fatty esters,proxylated & ethoxylated fatty acids, alcohols, or alkyl phenols, fattyesters series, ethoxylated fatty acids, Ethoxylated fatty esters andoils, alkanolamides series, amine oxides series, ethoxylated aminesand/or amides, POE stearic acid series, glycerol esters, glycol esters,ethoxylated oxazoline derivatives, monoglycerides and derivatives,lanolin based derivatives, amides, alkanolamides, amine oxides,hydrotropes, lecithin and Lecithin derivatives, phosphorous organicderivatives, sorbitan derivatives, protein based surfactants, allylpolyglycosides, thio and mercapto derivatives, imidazolines andimidazoline derivatives, cetearyl alcohols, emulsifying wax, octylphenol ethoxylate, sucrose and glucose esters and derivatives,dipropyleneglycol isocetech-20 acetate, phosphate esters,organo-phosphate ester, propylene glycol mono- and diesters of fats adfatty acids, mono- and diglycerides, partially hydrogenated vegetableoil with lecithin, BHT and citric acid, lauramine oxides, refined soyasterol, emulsified trichlorobenzene, emulsified aromatic and aliphaticsolvents and esters, emulsified proprietary aromatic, fatty esters,modified ethoxylate, phenoxy compound, ethylene oxide condensate,polyglyceryl dimerate, lecithin and lecithin derivatives,pentaerythrityl tetracaprylate/tetracaprate, lauramide MEA, linoleamideDEA, coco imidazoline, imidazolines and imidazoline derivatives,carboxylated alcohol or alkylphenol ethoxylates, ethoxylated arylphenols, and many others. Nonionic surfactants, such as Abex® seriesfrom Rhodia Inc., Actrafos® series from Georgia Pacific, Acconon® seriesfrom Abitec Corporation, Adsee® series from Witco Corp., Aldo® seriesfrom Lonza Inc., Amidex® series from Chemron Corp., Amodox series fromStepan Company, heterocyclic type products, and many other companies.Preferred nonionic surfactants are TAE 80 from BASF, Surforic L24-7 fromBASF and some others.

Suitable polymeric dispersants include, but are not limited to,polyethylene glycols, PEO polymers, PEO ether, PEO/PPO block polymers,polyether, polyoxyalkylated alcohol, polyoxyethylene styrenated phenylether, block copolymer of alkoxylated glycols, polysaccharides, alkylpolyglycosides, PEG, PEG corn glycerides, PEG palm kernel glycerides,polyacrylic acid copolymers, polyacryamides, polymethyl acrylic acid,polyoxyalkylene ether, polyamides, polyproxylated & ethoxylated fattyacids, alcohols, or alkyl phenols, polycarboxylate polymers, anypolymers comprising a hydrophilic side chain substituted polyimide orpolyamide composition, any polymers having a hydrophilic groups, such as—COOH, a derivative of —COOH, sulfonic acid, a derivative of sulfonicacid, amine, and epoxy. Preferred polymeric surfactants are polyvinylalcohols (PVOH), Polyvinyl pyrrolidone (PVP), and more.

Suitable silicone-based surfactants are dimethicone copolyols,polysiloxane polyether copolymer, cetyl dimethicone copolyol,polysiloxane polyalkyl polyether copolymers, silicone ethylene oxidecopolymers, silicone glycol, cocamide DEA, silicone glycol copolymers,such as Abil B series, Abil EM series, Abil WE series from GoldschmodtAG, Silwet series from Witco Corporation.

Adjunct Materials

Any number of additional ingredients can also be included as componentsin the various detergent and cleaning compositions described herein.These include other detergency builders, bleaches, bleach activators,suds boosters or suds suppressors, anti-tarnish and anti-corrosionagents, soil suspending agents, soil release agents, germicides, pHadjusting agents, non-builder alkalinity sources, chelating agents,smectite clays, enzymes, enzyme-stabilizing agents and perfumes. SeeU.S. Pat. No. 3,936,537.

Bleaching agents and activators are described in U.S. Pat. Nos.4,412,934 and 4,483,781. Chelating agents are also described in U.S.Pat. No. 4,663,071 from column 17, line 54 through column 18, line 68.Suds modifiers are also optional ingredients and are described in U.S.Pat. Nos. 3,933,672 and 4,136,045. Suitable smectite clays for useherein are described in U.S. Pat. No. 4,762,645 column 6, line 3 throughcolumn 7, line 24. Suitable additional detergency builders for useherein are enumerated in U.S. Pat. No. 3,936,537 at column 13, line 54through column 16, line 16, and in U.S. Pat. No. 4,663,071.

In yet another aspect of the present disclosure, the fabric carecompositions disclosed herein, may take the form of rinse added fabricconditioning compositions. Such compositions may comprise a fabricsoftening active and the dispersant polymer of the present disclosure,to provide a stain repellency benefit to fabrics treated by thecomposition, typically from about 0.00001 wt. % (0.1 ppm) to about 1 wt.% (10,000 ppm), or even from about 0.0003 wt. % (3 ppm) to about 0.03wt. % (300 ppm) based on total rinse added fabric conditioningcomposition weight. In another specific embodiment, the compositions arerinse added fabric conditioning compositions. Examples of typical rinseadded conditioning composition can be found in U.S. Provisional PatentApplication Ser. No. 60/687,582 filed on Oct. 8, 2004.

While not essential for the purposes of the present disclosure, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in various embodiments of the cleaning compositions and may bedesirably incorporated in certain embodiments of the disclosure, forexample to assist or enhance performance, for treatment of the substrateto be cleaned, or to modify the aesthetics of the composition as is thecase with perfumes, colorants, dyes or the like. It is understood thatsuch adjuncts are in addition to the components that were previouslylisted for any particular embodiment. The total amount of such adjunctsmay range from about 0.1% to about 50%, or even from about 1% to about30%, by weight of the cleaning composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable adjunct materials include, but are not limited to, polymers,for example cationic polymers, surfactants, builders, chelating agents,dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic materials, bleach activators, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282; 6,306,812; and6,326,348.

As stated, the adjunct ingredients are not essential to the cleaningcompositions. Thus, certain embodiments of the compositions do notcontain one or more of the following adjuncts materials: bleachactivators, surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic metal complexes, polymeric dispersing agents, clay and soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,additional perfumes and perfume delivery systems, structure elasticizingagents, fabric softeners, carriers, hydrotropes, processing aids and/orpigments. However, when one or more adjuncts are present, such one ormore adjuncts may be present as detailed below:

Surfactants—The compositions according to the present disclosure cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present disclosure can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds, ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the presentdisclosure may also include one or more dye transfer inhibiting agents.Suitable polymeric dye transfer inhibiting agents include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole (PVPVI),polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present disclosure can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand (“MRL”). As a practical matter, andnot by way of limitation, the compositions and cleaning processes hereincan be adjusted to provide on the order of at least one part per hundredmillion of the benefit agent MRL species in the aqueous washing medium,and may provide from about 0.005 ppm to about 25 ppm, from about 0.05ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of theMRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Preferred MRLs herein area special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. Suitabletransition metal MRLs are readily prepared by known procedures, such astaught, for example, in WO 00/32601, and U.S. Pat. No. 6,225,464.

EXAMPLES Surface Treatment Compositions Example 1 Preparation ofPolyorganosiloxane-Silicone Resin Mixtures 1-A. Preparation of a StableOil Mixture

13.2 g MQ silicone resin ([Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627), Mn=2700g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether(obtainable from Sigma-Aldrich Chemicals GmbH) by stirring and thenmixed with 76.3 g amine oil (viscosity of approximately 1000 mm²/sec at25° C., functional residues —(CH₂)₃NH(CH₂)NH₂, amine number 0.6 mmol/g,90% SiMe₃ end groups, 10% SiMe₂OH end groups) at 25° C. A clear,colorless solution with a viscosity of approximately 3000 mPa·s isobtained.

1-B. Preparation of a Stable Oil Mixture

13.2 g MQ silicone resin ([Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627), Mn=2700g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3 gamine oil (viscosity of approximately 500 mm²/sec at 25° C., functionalresidues —(CH₂)₃NH(CH₂)NH₂, amine number 0.6 mmol/g, 68% SiMe₃ endgroups, 25% SiMe₂OH end groups, 7% SiMe₂OMe end groups) at 25° C. Aclear, colorless solution with a viscosity of approximately 3000 mPa·sis obtained.

1-C. Preparation of a Stable Oil Mixture

13.2 g MQ silicone resin ([Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627), Mn=2700g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3 gamine oil (viscosity of approximately 1300 mm²/sec at 25° C., functionalresidues —(CH₂)₃NH(CH₂)NH₂, amine number 0.8 mmol/g, 60% SiMe₃ endgroups, 33% SiMe₂OH end groups, 7% SiMe₂OMe end groups) at 25° C. Aclear, colorless solution with a viscosity of approximately 3000 mPa·sis obtained.

1-D. Preparation of a Stable/Low Performance Oil Mixture

13.2 g MQ silicone resin ([Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627), Mn=2700g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether(Sigma-Aldrich Chemicals GmbH) by stirring and then mixed with 76.3 gamine oil (viscosity of approximately 2500 mm²/sec at 25° C., functionalresidues —(CH₂)₃NH(CH₂)NH₂, amine number 0.3 mmol/g, 72% SiMe₃ endgroups, 26% SiMe₂OH end groups, 2% SiMe₂OMe end groups) at 25° C. Aclear, colorless solution with a viscosity of approximately 3000 mPa·sis obtained.

1-E. Preparation of an Unstable Oil Mixture, not in Accordance with theInvention

13.2 g MQ silicone resin ([Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627), Mn=2700g/mol) is dissolved in 10.5 g ethylene glycol monohexyl ether(Sigma-Aldrich Chemicals GmbH) by stifling and then mixed with 76.3 gamine oil (viscosity of approximately 2800 mm²/sec at 25° C., functionalresidues —(CH₂)₃NH(CH₂)NH₂, amine number 0.6 mmol/g, 47% SiMe₃ endgroups, 45% SiMe₂OH end groups, 8% SiMe₂OMe end groups) at 25° C. Aclear, colorless solution with a viscosity of approximately 3000 mPa·sis obtained. This mixture formed a gel after 3 days and was no longerusable.

Example 2 Application Examples

2-A. The mixtures prepared above were for applications testing. The saidoil mixture was diluted with isopropyl alcohol to a solids content of2%. The solutions were sprayed onto cotton fabrics and the fabrics wereline dried. After drying, time to wick was measured on all fabricsaccording to the Time to Wick (T2W) testing method protocol describedbelow.

Water T2W Untreated 0 second Example A >20 minute Example B >20 minuteExample C >20 minute Example D >20 minute Example E Not applicable(unstable)2-B. The above mixture was mixed with emulsifiers (fatty alcoholethoxylate with 6 EO) and acetic acid and then water to make 35%emulsions. The emulsions were diluted into 2% solution with water.Cotton fabric was dipped in the solution and then line dried. The timeto wick was measured on the fabrics according to the T2W testing method.

Water T2W Untreated 0 second Example A >20 minute Example B >20 minuteExample C >20 minute Example D >20 minute Example E Not applicable(unstable)

According to certain embodiments, the polyorganosiloxane-silicone resinmixture of the present disclosure may also be incorporated into anysurface treatment or cleaning composition, such as, but not limited to,a fabric care composition, a dish cleaning composition, a home surfacecare composition or a personal care composition. Examples of treatmentand cleaning compositions include, but are not limited to, liquidlaundry detergents, solid laundry detergents, laundry soap products,laundry spray treatment products, laundry pre-treatment products, handdish washing detergents, automatic dishwashing detergents, a beauty caredetergent, hard surface cleaning detergents, carpet cleaning detergents,a shampoo, and a household cleaning detergent. Examples of fabric carecompositions suitable for the present disclosure include, but are notlimited to, liquid laundry detergents, heavy duty liquid laundrydetergents, solid laundry detergents, laundry soap products, laundryspray treatment products, laundry pre-treatment products, laundry soakproducts, heavy duty liquid detergents, and rinse additives. Examples ofsuitable dish cleaning compositions include, but are not limited to,automatic dishwasher detergents, detergents for hand washing of dishes,liquid dish soap, and solid granular dish soap. Examples of suitablehome care compositions include, but are not limited to, rug or carpetcleaning compositions, hard surface cleaning detergents, floor cleaningcompositions, window cleaning compositions, toilet and bathroom cleaningcompositions, household cleaning detergents, and car washing detergents.Examples of suitable personal care compositions include, but are notlimited to, beauty care detergents, beauty bars, bar soap, bath beads,bath soaps, hand washing compositions, body washes and soaps, shampoo,conditioners, cosmetics, hair removal compositions, and oral carecompositions.

Example 3 Liquid Laundry Additive Compositions

The above mixtures were mixed with emulsifiers (fatty alcohol ethoxylatewith 6 EO) and acetic acid and then water to make 35% emulsions. Theemulsions were then made into products with the following formulation.The formulated products were used in the rinse cycle in the washingmachine with loaded cotton garments. Normal wash conditions were usedand Tide detergent was used in the wash cycle.

Formula (w/w active %) Si Fluid-Resin Mixtures from Example 1 10.67Cationic Starch (Maize, MW 1,500,000 0.72 Daltons, charge density 0.42meq/g, amylase 28%) DTDMAC 1.33 Perfume: 0.20 Preservant: Proxel 0.015

Cotton fabric was dipped in the solution and then line dried. The timeto wick was measured on the fabrics according to the T2W testing method.

Water T2W Untreated 0 second Product/Example A 977 secondProduct/Example B 1200 second Product/Example C >20 minuteProduct/Example D 7 second Product/Example E Not applicable (unstable)

Liquid laundry additive compositions 1-9 detailed below have detailedpercentages based on 100% active basis.

Ingredient 1 2 3 4 5 6 7 8 9 Dosage 30 g 30 g 30 g 30 g 30 g 30 g 30 g30 g 30 g Wacker HC306 6.00% 6.00% 6.00% 6.00% 6.00% 12.00% 12.00%12.00% 12.00% Akzo Nobel 1.20% 1.20% 1.20% 1.20% 1.20% 1.20% 1.20% 1.20%1.20% EXP5617 TAE80 0.25% 0.25% 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%0.25% Proxel GXL 0.02% 0.02% 0.02% 0.02% 0.02% 0.02% 0.02% 0.02% 0.02%Best B perfume 0.40% 0.40% 0.40% 0.40% 0.40% 0.40% 0.40% 0.40% 0.40%Butyl Carbitol 3.00% 3.00% 3.00% 3.00% 3.00% 2.00% 2.00% 2.00% 2.00%Polyamine N- 0.00% 0.83% 1.67% 3.34% 5.00% 0.00% 1.67% 3.34% 5.00% oxideT2W (sec.) 7 14 37 73 78 15 75 149 282

Example 4 Liquid Detergent Compositions

The treatment or cleaning compositions herein, such as, but not limitedto liquid detergent compositions, may take the form of an aqueoussolution or uniform dispersion or suspension of surfactant and water,polyorganosiloxane-silicone resin mixture, and certain optional adjunctingredients, some of which may normally be in solid form, that have beencombined with the normally liquid components of the composition.Suitable surfactants may be anionic, nonionic, cationic, zwitterionicand/or amphoteric surfactants. In one embodiment, the cleaningcomposition comprises anionic surfactant, nonionic surfactant, ormixtures thereof.

Suitable anionic surfactants may be any of the conventional anionicsurfactant types typically used in cleaning compositions, such as liquidor solid detergent products. Such surfactants include the alkyl benzenesulfonic acids and their salts as well as alkoxylated or non-alkoxylatedalkyl sulfate materials. Exemplary anionic surfactants are the alkalimetal salts of C₁₀-C₁₆ alkyl benzene sulfonic acids, preferably C₁₁-C₁₄alkyl benzene sulfonic acids. In one aspect, the alkyl group is linear.Such linear alkyl benzene sulfonates are known as “LAS”. Suchsurfactants and their preparation are described for example in U.S. Pat.Nos. 2,220,099 and 2,477,383. Especially preferred are the sodium andpotassium linear straight chain alkylbenzene sulfonates in which theaverage number of carbon atoms in the alkyl group is from about 11 to14. Sodium C₁₁-C₁₄, e.g., C₁₂ LAS is a specific example of suchsurfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In a specificembodiment, R′ is C₁₀-C₁₈ alkyl, n is from about 1 to 15, and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium. In morespecific embodiments, R′ is a C₁₂-C₁₆, n is from about 1 to 6, and M issodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the cleaning compositions ofthis disclosure and used as or in any anionic surfactant component whichmay be present. Specific examples of non-alkoxylated, e.g.,non-ethoxylated, alkyl ether sulfate surfactants are those produced bythe sulfation of higher C₈-C₂₀ fatty alcohols. Conventional primaryalkyl sulfate surfactants have the general formula: R″OSO₃ ⁻M⁺ whereinR″ is typically a linear C₈-C₂₀ hydrocarbyl group, which may be straightchain or branched chain, and M is a water-solubilizing cation. Inspecific embodiments, R″ is a C₁₀-C₁₅ alkyl, and M is alkali metal, morespecifically R″ is C₁₂-C₁₄ and M is sodium.

Specific, nonlimiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3)-alkyl sulfates having Formulae (XII) and (XIII):

wherein M in Formulae (XII) and (XIII) is hydrogen or a cation whichprovides charge neutrality, and all M units, whether associated with asurfactant or adjunct ingredient, can either be a hydrogen atom or acation depending upon the form isolated by the artisan or the relativepH of the system wherein the compound is used, with non-limitingexamples of preferred cations including sodium, potassium, ammonium, andmixtures thereof, and x in Formula XII is an integer of at least about7, preferably at least about 9, and y in Formula XIII is an integer ofat least 8, preferably at least about 9; d) C₁₀-C₁₈ alkyl alkoxysulfates (AE_(x)S) wherein preferably x in Formula XII is from 1-30; e)C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5 ethoxyunits; f) mid-chain branched alkyl sulfates as discussed in U.S. Pat.Nos. 6,020,303 and 6,060,443; g) mid-chain branched alkyl alkoxysulfates as discussed in U.S. Pat. Nos. 6,008,181 and 6,020,303; h)modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO99/07656, WO 00/23549, and WO 00/23548.; i) methyl ester sulfonate(MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. Preferred for use in the liquid detergent productsherein are those nonionic surfactants which are normally liquid.Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R⁷(C_(m)H_(2m)O)_(n)OH wherein R⁷ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.Preferably R⁷ is an alkyl group, which may be primary or secondary, thatcontains from about 9 to 15 carbon atoms, more preferably from about 10to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcoholswill also be ethoxylated materials that contain from about 2 to 12ethylene oxide moieties per molecule, more preferably from about 3 to 10ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17. More preferably, the HLBof this material will range from about 6 to 15, most preferably fromabout 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have beenmarketed under the tradename NEODOL® by the Shell Chemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R′″(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula,R′″ is a relatively long-chain hydrocarbyl moiety which can be saturatedor unsaturated, linear or branched, and can contain from 8 to 20,preferably from 10 to 16 carbon atoms, and is more preferably C₁₂-C₁₆primary alkyl. R′ is a short-chain moiety, preferably selected fromhydrogen, methyl and —CH₂OH. When x+y+z is different from 0, EO isethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxidesurfactants are illustrated by C₁₂-C₁₄ alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants; b) C₆-C₁₂ alkylphenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as PLURONIC® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x is 1-30, as discussed in U.S. Pat.Nos. 6,153,577; 6,020,303; and 6,093,856; f) alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647; specifically alkylpolyglycosidesas discussed in U.S. Pat. Nos. 4,483,780 and 4,483,779; g) polyhydroxyfatty acid amides as discussed in U.S. Pat. No. 5,332,528; WO 92/06162;WO 93/19146; WO 93/19038; and WO 94/09099; and h) ether cappedpoly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No.6,482,994 and WO 01/42408.

In the laundry detergent compositions and other cleaning compositionsherein, the detersive surfactant component may comprise combinations ofanionic and nonionic surfactant materials. When this is the case, theweight ratio of anionic to nonionic will typically range from 10:90 to90:10, more typically from 30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002; WO 98/35003; WO 98/35004; WO 98/35005; and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042;4,239,660; 4,260,529; and 6,022,844; and e) amino surfactants asdiscussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specifically amidopropyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include: derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678at column 19, line 38 through column 22, line 48, for examples ofzwitterionic surfactants; betaine, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈-C₁₈ (preferably C₁₂-C₁₈) amineoxides and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈-C₁₈, preferably C₁₀-C₁₄.

Non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents contains at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 at column 19, lines 18-35, for examples of ampholyticsurfactants.

The cleaning compositions disclosed herein may be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stablecleaning composition. In one aspect, a liquid matrix is formedcontaining at least a major proportion, or even substantially all, ofthe liquid components, e.g., nonionic surfactant, the non-surface activeliquid carriers and other optional liquid components, with the liquidcomponents being thoroughly admixed by imparting shear agitation to thisliquid combination. For example, rapid stirring with a mechanicalstirrer may usefully be employed. While shear agitation is maintained,substantially all of any anionic surfactant and the solid ingredientscan be added. Agitation of the mixture is continued, and if necessary,can be increased at this point to form a solution or a uniformdispersion of insoluble solid phase particulates within the liquidphase. After some or all of the solid-form materials have been added tothis agitated mixture, particles of any enzyme material to be included,e.g., enzyme prills are incorporated. As a variation of the compositionpreparation procedure described above, one or more of the solidcomponents may be added to the agitated mixture as a solution or slurryof particles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In another aspect of producing liquid cleaning compositions, thepolyorganosiloxane-silicone resin mixture may first be combined with oneor more liquid components to form a polyorganosiloxane-silicone resinmixture premix, and this polyorganosiloxane-silicone resin mixturepremix is added to a composition formulation containing a substantialportion, for example more than 50% by weight, more than 70% by weight,or even more than 90% by weight, of the balance of components of thecleaning composition. For example, in the methodology described above,both the polyorganosiloxane-silicone resin mixturepolyorganosiloxane-silicone resin mixture premix and the enzymecomponent are added at a final stage of component additions. In anotheraspect, the polyorganosiloxane-silicone resin mixture is encapsulatedprior to addition to the detergent composition, the encapsulatedpolyorganosiloxane-silicone resin mixture is suspended in a structuredliquid, and the suspension is added to a composition formulationcontaining a substantial portion of the balance of components of thecleaning composition.

Heavy Duty Liquid Laundry Detergent Formulations

In this Example, three sample formulations for a heavy duty liquid (HDL)laundry detergent are prepared using the polyorganosiloxane-siliconeresin mixture according to embodiments of the present disclosure. Thepolyorganosiloxane-silicone resin mixture is added to the formulationsin an amount ranging from 0.5% to 10.0% by weight.

A B C D E Ingredient Wt % Wt % Wt % Wt % Wt % Sodium alkyl ether 20.520.5 20.5 sulfate C12-15 Alkyl 9.0 Polyethoxylate (1.1) Sulfonic AcidBranched alcohol sulfate 5.8 5.8 5.8 Linear alkylbenzene 2.5 2.5 2.5 1.08.0 sulfonic acid Alkyl ethoxylate 0.8 0.8 0.8 1.5 6.0 Amine oxide 0 0.52 1.0 Citric acid 3.5 3.5 3.5 2.0 2.5 Fatty acid 2.0 2.0 2.0 5.5Protease 0.7 0.7 0.7 0.4 0.4 Amylase 0.37 0.37 0.37 0.08 0.08 Mannanase0.03 0.03 Borax (38%) 3.0 3.0 3.0 1.0 MEA Borate 1.5 Calcium and sodium0.22 0.22 0.22 0.7 formate Amine ethoxylate 1.2 0.5 1.0 1.0 1.5 polymersZwitterionic amine 1.0 2.0 1.0 ethoxylate polymer Polyorganosiloxane 0.51.0 2.0 1.0 1.0 Fluid-Silicone Resin Mixture¹ DTPA² 0.25 0.25 0.25 0.30.3 Fluorescent whitening 0.2 0.2 0.2 agent Ethanol 2.9 2.9 2.9 1.5 1.5Propylene Glycol 3.0 5.0 Propanediol 5.0 5.0 5.0 Diethylene glycol 2.562.56 2.56 Polyethylene glycol 4000 0.11 0.11 0.11 Monoethanolamine 2.72.7 2.7 1.0 0.5 Sodium hydroxide (50%) 3.67 3.67 3.67 1.4 1.4 Sodiumcumene sulfonate 0 0.5 1 0.7 Silicone suds suppressor 0.01 0.01 0.010.02 Perfume 0.5 0.5 0.5 0.30 0.3 Dye 0.01 0.01 0.01 0.016 0.016Opacifier³ 0.01 0.01 0.01 Water balance balance balance balance balance100.0% 100.0% 100.0% 100.0% 100.0% ¹Polyorganosiloxane Fluid-SiliconeResin Mixture of Example 1 ²Diethylenetriaminepentaacetic acid, sodiumsalt ³Acusol OP 301

Example 5 Granular Laundry Detergent Compositions

In another aspect of the present disclosure, the fabric carecompositions disclosed herein, may take the form of granular laundrydetergent compositions. Such compositions comprise the dispersantpolymer of the present disclosure to provide soil and stain removal andanti-redeposition, suds boosting, and/or soil release benefits to fabricwashed in a solution containing the detergent. Typically, the granularlaundry detergent compositions are used in washing solutions at a levelof from about 0.0001% to about 0.05%, or even from about 0.001% to about0.01% by weight of the washing solution.

Detergent compositions may be in the form of a granule. Typicalcomponents of granular detergent compositions include but are notlimited to surfactants, builders, bleaches, bleach activators and/orother bleach catalysts and/or boosters, enzymes, enzyme stabilizingagents, soil suspending agents, soil release agents, pH adjusting agentsand/or other electrolytes, suds boosters or suds suppressers,anti-tarnish and anticorrosion agents, non-builder alkalinity sources,chelating agents, organic and inorganic fillers, solvents, hydrotropes,clays, silicones, flocculant, dye transfer inhibitors, photobleaches,fabric integrity agents, effervesence-generating agents, processing aids(non-limiting examples of which include binders and hydrotropes),germicides, brighteners, dyes, and perfumes. Granular detergentcompositions typically comprise from about 1% to 95% by weight of asurfactant. Detersive surfactants utilized can be of the anionic,nonionic, cationic, zwitterionic, ampholytic, amphoteric, or catanionictype or can comprise compatible mixtures of these types.

Granular detergents can be made by a wide variety of processes,non-limiting examples of which include spray drying, agglomeration,fluid bed granulation, marumarisation, extrusion, or a combinationthereof. Bulk densities of granular detergents generally range fromabout 300 g/l-1000 g/l. The average particle size distribution ofgranular detergents generally ranges from about 250 microns-1400microns.

Granular detergent compositions of the present disclosure may includeany number of conventional detergent ingredients. For example, thesurfactant system of the detergent composition may include anionic,nonionic, zwitterionic, ampholytic and cationic classes and compatiblemixtures thereof. Detergent surfactants for granular compositions aredescribed in U.S. Pat. Nos. 3,664,961 and 3,919,678. Cationicsurfactants include those described in U.S. Pat. Nos. 4,222,905 and4,239,659.

Non-limiting examples of surfactant systems include the conventionalC₁₁-C₁₈ alkyl benzene sulfonates (“LAS”) and primary, branched-chain andrandom C₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈ secondary (2,3) alkylsulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺)CH₃ andCH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where x and (y+1) are integers of atleast about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”;especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀-C₁₈ glycerol ethers,the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. Ifdesired, the conventional nonionic and amphoteric surfactants such asthe C₁₂-C₁₈ alkyl ethoxylates (“AE”) including the so-called narrowpeaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines andsulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides, and the like, canalso be included in the surfactant system. The C₁₀-C₁₈ N-alkylpolyhydroxy fatty acid amides can also be used. See WO 92/06154. Othersugar-derived surfactants include the N-alkoxy polyhydroxy fatty acidamides, such as C₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propylthrough N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀conventional soaps may also be used. If high sudsing is desired, thebranched-chain C₁₀-C₁₆ soaps may be used. Mixtures of anionic andnonionic surfactants are especially useful. Other conventional usefulsurfactants are listed in standard texts.

The cleaning composition can, and in certain embodiments preferablydoes, include a detergent builder. Builders are generally selected fromthe various water-soluble, alkali metal, ammonium or substitutedammonium phosphates, polyphosphates, phosphonates, polyphosphonates,carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates,carboxylates, and polycarboxylates. Preferred are the alkali metals,especially sodium, salts of the above. Preferred for use herein are thephosphates, carbonates, silicates, C₁₀-C₁₈ fatty acids,polycarboxylates, and mixtures thereof. More preferred are sodiumtripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- anddi-succinates, sodium silicate, and mixtures thereof.

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphates. Examples of polyphosphonate builders are the sodium andpotassium salts of ethylene diphosphonic acid, the sodium and potassiumsalts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium andpotassium salts of ethane-1,1,2-triphosphonic acid. Other phosphorusbuilder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,422,137; 3,400,176; and 3,400,148. Examples ofnon-phosphorus, inorganic builders are sodium and potassium carbonate,bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicateshaving a weight ratio of SiO₂ to alkali metal oxide of from about 0.5 toabout 4.0, preferably from about 1.0 to about 2.4. Water-soluble,non-phosphorus organic builders useful herein include the various alkalimetal, ammonium and substituted ammonium polyacetates, carboxylates,polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate andpolycarboxylate builders are the sodium, potassium, lithium, ammoniumand substituted ammonium salts of ethylene diamine tetraacetic acid,nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, and citric acid.

Polymeric polycarboxylate builders are set forth in U.S. Pat. No.3,308,067. Such materials include the water-soluble salts of homo- andcopolymers of aliphatic carboxylic acids such as maleic acid, itaconicacid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid andmethylenemalonic acid. Some of these materials are useful as thewater-soluble anionic polymer as hereinafter described, but only if inintimate admixture with the non-soap anionic surfactant. Other suitablepolycarboxylates for use herein are the polyacetal carboxylatesdescribed in U.S. Pat. Nos. 4,144,226 and 4,246,495.

Water-soluble silicate solids represented by the formula SiO₂.M₂O, Mbeing an alkali metal, and having a SiO₂:M₂O weight ratio of from about0.5 to about 4.0, are useful salts in the detergent granules of thisdisclosure at levels of from about 2% to about 15% on an anhydrousweight basis. Anhydrous or hydrated particulate silicate can beutilized, as well.

Various techniques for forming cleaning compositions in such solid formsare well known in the art and may be used herein. In one aspect, whenthe cleaning composition, such as a fabric care composition, is in theform of a granular particle, the polyorganosiloxane-silicone resinmixture is provided in particulate form, optionally including additionalbut not all components of the cleaning composition. Thepolyorganosiloxane-silicone resin mixture particulate is combined withone or more additional particulates containing a balance of componentsof the cleaning composition. Further, the polyorganosiloxane-siliconeresin mixture, optionally including additional but not all components ofthe cleaning composition may be provided in an encapsulated form, andthe polyorganosiloxane-silicone resin mixture encapsulate is combinedwith particulates containing a substantial balance of components of thecleaning composition.

Powder Laundry Detergent Formulations

In this Example, four sample formulations for a powder laundry detergentare prepared using the polysiloxane-silicone resin mixture according toembodiments of the present disclosure. The polyorganosiloxane-siliconeresin mixture is added to the formulations in an amount ranging from1.0% to 10.0% by weight.

A B C D Ingredients Wt. % Wt. % Wt. % Wt. % Sodium alkylben- 16.000014.0000 12.0000 7.9 zenesulfonate Sodium alkyl — — — 4.73 alcoholethoxy- late (3) sulfate Sodium mid-cut 1.5000 1.5000 — alkyl sulfateAlkyl dimethyl — — — 0.5 hydroxyethyl quaternary amine (chloride) Alkylethoxylate 1.3000 1.3000 1.3000 — Polyamine¹ — — — 0.79 Nonionic 1.00001.0000 1.0000 1.0 Polymer² Carboxymethyl- 0.2000 0.2000 0.2000 1.0cellulose Sodium — — — — polyacrylate Sodium 0.7000 0.7000 0.7000 3.5polyacrylate/ maleate polymer Polyorgano- 1.0000 1.0000 1.0000 3.0000siloxane Fluid-Silicone Resin Mixture³ Sodium 10.0000 5.0000 — —tripolyphosphate Zeolite 16.0000 16.0000 16.0000 — Citric Acid — — — 5.0Sodium 12.5000 12.5000 12.5000 25.0 Carbonate Sodium Silicate 4.0 4.04.0 — Enzymes⁴ 0.30 0.30 0.30 0.5 Minors including balance balancebalance balance moisture⁵ ¹Hexamethylenediamine ethoxylated to 24 unitsfor each hydrogen atom bonded to a nitrogen, quaternized. ²Comb polymerof polyethylene glycol and polyvinylacetate ³PolyorganosiloxaneFluid-Silicone Resin Mixture of Example 1 ⁴Enzyme cocktail selected fromknown detergent enzymes including amylase, cellulase, protease, andlipase. ⁵Balance to 100% can, for example, include minors like opticalbrightener, perfume, suds suppresser, soil dispersant, soil releasepolymer, chelating agents, bleach additives and boosters, dye transferinhibiting agents, aesthetic enhancers (example: Speckles), additionalwater, and fillers, including sulfate, CaCO₃, talc, silicates, etc.

Example 6 Automatic Dishwasher Detergent Formulation

In this Example, five sample formulations for an automatic dishwasherdetergent are prepared using the polyorganosiloxane-silicone resinmixture according to embodiments of the present disclosure. Thepolyorganosiloxane-silicone resin mixture is added to the formulationsin an amount ranging from 0.05% to 15% by weight.

A B C D E Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Polymer 0.5 5 6 5 5dispersant¹ Carbonate 35 40 40 35-40 35-40 Sodium tri- 0 6 10  0-10 0-10 polyphosphate Silicate solids 6 6 6 6 6 Bleach and 4 4 4 4 4Bleach activators Enzymes 0.3-0.6 0.3-0.6 0.3-0.6 0.3-0.6 0.3-0.6Disodium ci- 0 0 0  2-20 0 trate dihydrate Nonionic 0 0 0 0 0.8-5  surfactant² Polyorgano- 0.05-15   0.05-15   0.05-15   0.05-15  0.05-15   siloxane Fluid-Silicone Resin Mixture³ Water, sulfate, BalanceBalance Balance Balance Balance perfume, dyes to 100% to 100% to 100% to100% to 100% and other adjuncts ¹Anionic polymers such as Acuso,Alcosperse and other modified polyacrylic acid polymers. ²Such as SLF-18polytergent from Olin Corporation ³PolyorganosiloxaneFluid-SiliconeResin Mixture of Example 1

Example 7 Liquid Dishwashing Liquid Liquid Dish Handwashing Detergents

Composition A B C₁₂₋₁₃ Natural AE0.6S 270 240 C₁₀₋₁₄ mid-branched AmineOxide — 6.0 C₁₂₋₁₄ Linear Amine Oxide 6.0 — SAFOL ® 23 Amine Oxide 1.01.0 C₁₁E₉ Nonionic ¹ 2.0 2.0 Ethanol 4.5 4.5 Sodium cumene sulfonate 1.61.6 Polypropylene glycol 2000 0.8 0.8 NaCl 0.8 0.8 1,3 BAC Diamine² 0.50.5 Polyorganosiloxane Fluid-Silicone 0.05-15 0.05-15 Resin Mixture³Water Balance Balance ¹ Nonionic may be either C₁₁ Alkyl ethoxylatedsurfactant containing 9 ethoxy groups. ²1,3, BAC is 1,3bis(methylamine)-cyclohexane. ³Polyorganosiloxane Fluid-Silicone ResinMixture of Example 1

Example 8 Unit Dose

The detergent product of the present invention may comprise awater-soluble pouch, more preferably a multi-compartment water-solublepouch. Such a pouch comprises a water-soluble film and at least a first,and optionally a second compartment. The first compartment comprises afirst composition, comprising an opacifier and an antioxidant. Thesecond compartment comprises a second compartment. Preferably the pouchcomprises a third compartment and a third composition. The optionallysecond and third compositions are preferably visibly distinct from eachother and the first composition.

Optionally, a difference in aesthetic appearance may be achieved in anumber of ways. However the first compartment of the pouch may comprisean opaque liquid composition. The compartments of the pouch may be thesame size or volume. Alternatively, the compartments of the pouch mayhave different sizes, with different internal volumes.

The compartments may also be different from one another in terms oftexture. Hence one compartment may be glossy, while the other is matt.This can be readily achieved as one side of a water-soluble film isoften glossy, while the other has a matt finish. Alternatively the filmused to make a compartment may be treated in a way so as to emboss,engrave or print the film. Embossing may be achieved by adheringmaterial to the film using any suitable means described in the art.Engraving may be achieved by applying pressure onto the film using anysuitable technique available in the art. Printing may be achieved usingany suitable printer and process available in the art. Alternatively,the film itself may be colored, allowing the manufacturer to selectdifferent colored films for each compartment. Alternatively the filmsmay be transparent or translucent and the composition contained withinmay be colored.

Unit dose compositions may have compartments which can be separate, butare preferably conjoined in any suitable manner. Most preferably thesecond and optionally third or subsequent compartments are superimposedon the first compartment. In one embodiment, the third compartment maybe superimposed on the second compartment, which is in turn superimposedon the first compartment in a sandwich configuration. Alternatively thesecond and third compartments are superimposed on the first compartment.However it is also equally envisaged that the first, second andoptionally third and subsequent compartments may be attached to oneanother in a side by side relationship. The compartments may be packedin a string, each compartment being individually separable by aperforation line. Hence each compartment may be individually torn-offfrom the remainder of the string by the end-user, for example, so as topre-treat or post-treat a fabric with a composition from a compartment.

In a preferred embodiment the pouch may comprise three compartmentsconsisting of a large first compartment and two smaller compartments.The second and third smaller compartments are superimposed on the firstlarger compartment. The size and geometry of the compartments are chosensuch that this arrangement is achievable.

The geometry of the compartments may be the same or different. In apreferred embodiment the second and optionally third compartment have adifferent geometry and shape to the first compartment. In thisembodiment the second and optionally third compartments are arranged ina design on the first compartment. Said design may be decorative,educative, illustrative for example to illustrate a concept orinstruction, or used to indicate origin of the product. In a preferredembodiment the first compartment is the largest compartment having twolarge faces sealed around the perimeter. The second compartment issmaller covering less than 75%, more preferably less than 50% of thesurface area of one face of the first compartment. In the embodimentwherein there is a third compartment, the above structure is the samebut the second and third compartments cover less than 60%, morepreferably less than 50%, even more preferably less than 45% of thesurface area of one face of the first compartment.

The pouch is preferably made of a film material which is soluble ordispersible in water, and has a water-solubility of at least 50%,preferably at least 75% or even at least 95%, as measured by the methodset out here after using a glass-filter with a maximum pore size of 20microns:

50 grams±0.1 gram of pouch material is added in a pre-weighed 400 mlbeaker and 245 ml±1 ml of distilled water is added. This is stirredvigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then,the mixture is filtered through a folded qualitative sintered-glassfilter with a pore size as defined above (max. 20 micron). The water isdried off from the collected filtrate by any conventional method, andthe weight of the remaining material is determined (which is thedissolved or dispersed fraction). Then, the percentage solubility ordispersability can be calculated.

Preferred pouch materials are polymeric materials, preferably polymerswhich are formed into a film or sheet. The pouch material can, forexample, be obtained by casting, blow-moulding, extrusion or blownextrusion of the polymeric material, as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for useas pouch material are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose,cellulose ethers, cellulose esters, cellulose amides, polyvinylacetates, polycarboxylic acids and salts, polyaminoacids or peptides,polyamides, polyacrylamide, copolymers of maleic/acrylic acids,polysaccharides including starch and gelatine, natural gums such asxanthum and carragum. More preferred polymers are selected frompolyacrylates and water-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%. The polymer canhave any weight average molecular weight, preferably from about 1000 to1,000,000, more preferably from about 10,000 to 300,000 yet morepreferably from about 20,000 to 150,000.

Mixtures of polymers can also be used as the pouch material. This can bebeneficial to control the mechanical and/or dissolution properties ofthe compartments or pouch, depending on the application thereof and therequired needs. Suitable mixtures include for example mixtures whereinone polymer has a higher water-solubility than another polymer, and/orone polymer has a higher mechanical strength than another polymer. Alsosuitable are mixtures of polymers having different weight averagemolecular weights, for example a mixture of PVA or a copolymer thereofof a weight average molecular weight of about 10,000-40,000, preferablyaround 20,000, and of PVA or copolymer thereof, with a weight averagemolecular weight of about 100,000 to 300,000, preferably around 150,000.Also suitable herein are polymer blend compositions, for examplecomprising hydrolytically degradable and water-soluble polymer blendssuch as polylactide and polyvinyl alcohol, obtained by mixingpolylactide and polyvinyl alcohol, typically comprising about 1-35% byweight polylactide and about 65% to 99% by weight polyvinyl alcohol.Preferred for use herein are polymers which are from about 60% to about98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improvethe dissolution characteristics of the material.

Naturally, different film material and/or films of different thicknessmay be employed in making the compartments of the present invention. Abenefit in selecting different films is that the resulting compartmentsmay exhibit different solubility or release characteristics.

Most preferred pouch materials are PVA films known under the tradereference Monosol M8630, as sold by Chris-Craft Industrial Products ofGary, Ind., US, and PVA films of corresponding solubility anddeformability characteristics. Other films suitable for use hereininclude films known under the trade reference PT film or the K-series offilms supplied by Aicello, or VF-HP film supplied by Kuraray.

The pouch material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticizers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

For reasons of deformability pouches or pouch compartments containing acomponent which is liquid will preferably contain an air bubble having avolume of up to about 50%, preferably up to about 40%, more preferablyup to about 30%, more preferably up to about 20%, more preferably up toabout 10% of the volume space of said compartment.

The water soluble pouch may be made using any suitable equipment andmethod. Single compartment pouches are made using vertical, butpreferably horizontal form filling techniques commonly known in the art.The film is preferably dampened, more preferably heated to increase themalleability thereof. Even more preferably, the method also involves theuse of a vacuum to draw the film into a suitable mould. The vacuumdrawing the film into the mould can be applied for 0.2 to 5 seconds,preferably 0.3 to 3 or even more preferably 0.5 to 1.5 seconds, once thefilm is on the horizontal portion of the surface. This vacuum maypreferably be such that it provides an under-pressure of between −100mbar to −1000 mbar, or even from −200 mbar to −600 mbar.

The moulds, in which the pouches are made, can have any shape, length,width and depth, depending on the required dimensions of the pouches.The moulds can also vary in size and shape from one to another, ifdesirable. For example, it may be preferred that the volume of the finalpouches is between 5 and 300 ml, or even 10 and 150 ml or even 20 and100 ml and that the mould sizes are adjusted accordingly.

Heat can be applied to the film, in the process commonly known asthermoforming, by any means. For example the film may be heated directlyby passing it under a heating element or through hot air, prior tofeeding it onto the surface or once on the surface. Alternatively it maybe heated indirectly, for example by heating the surface or applying ahot item onto the film. Most preferably the film is heated using aninfra red light. The film is preferably heated to a temperature of 50 to120° C., or even 60 to 90° C. Alternatively, the film can be wetted byany mean, for example directly by spraying a wetting agent (includingwater, solutions of the film material or plasticizers for the filmmaterial) onto the film, prior to feeding it onto the surface or once onthe surface, or indirectly by wetting the surface or by applying a wetitem onto the film.

Once a film has been heated/wetted, it is drawn into an appropriatemould, preferably using a vacuum. The filling of the molded film can bedone by any known method for filling (preferably moving) items. The mostpreferred method will depend on the product form and speed of fillingrequired. Preferably the molded film is filled by in-line fillingtechniques. The filled, open pouches are then closed, using a secondfilm, by any suitable method. Preferably, this is also done while inhorizontal position and in continuous, constant motion. Preferably theclosing is done by continuously feeding a second film, preferablywater-soluble film, over and onto the open pouches and then preferablysealing the first and second film together, typically in the areabetween the moulds and thus between the pouches.

Preferred methods of sealing include heat sealing, solvent welding, andsolvent or wet sealing. It is preferred that only the area which is toform the seal, is treated with heat or solvent. The heat or solvent canbe applied by any method, preferably on the closing material, preferablyonly on the areas which are to form the seal. If solvent or wet sealingor welding is used, it may be preferred that heat is also applied.Preferred wet or solvent sealing/welding methods include applyingselectively solvent onto the area between the moulds, or on the closingmaterial, by for example, spraying or printing this onto these areas,and then applying pressure onto these areas, to form the seal. Sealingrolls and belts as described above (optionally also providing heat) canbe used, for example.

The formed pouches can then be cut by a cutting device. Cutting can bedone using any known method. It may be preferred that the cutting isalso done in continuous manner, and preferably with constant speed andpreferably while in horizontal position. The cutting device can, forexample, be a sharp item or a hot item, whereby in the latter case, thehot item ‘burns’ through the film/sealing area.

The different compartments of a multi-compartment pouch may be madetogether in a side-by-side style and consecutive pouches are not cut.Alternatively, the compartments can be made separately.

According to this process and preferred arrangement, the pouches aremade according to the process comprising the steps of: a) forming anfirst compartment (as described above); b) forming a recess within someor all of the closed compartment formed in step a), to generate a secondmoulded compartment superposed above the first compartment; c) fillingand closing the second compartments by means of a third film; d) sealingsaid first, second and third films; and e) cutting the films to producea multi-compartment pouch.

Said recess formed in step b) is preferably achieved by applying avacuum to the compartment prepared in step a). Alternatively the second,and optionally third, compartment(s) can be made in a separate step andthen combined with the first compartment as described in our co-pendingapplication EP 08101442.5 which is incorporated herein by reference. Aparticularly preferred process comprises the steps of: a) forming afirst compartment, optionally using heat and/or vacuum, using a firstfilm on a first forming machine; b) filling said first compartment witha first composition; c) on a second forming machine, deforming a secondfilm, optionally using heat and vacuum, to make a second and optionallythird moulded compartment; d) filling the second and optionally thirdcompartments; e) sealing the second and optionally third compartmentusing a third film; f) placing the sealed second and optionally thirdcompartments onto the first compartment; g) sealing the first, secondand optionally third compartments; and h) cutting the films to produce amulti-compartment pouch

The first and second forming machines are selected based on theirsuitability to perform the above process. The first forming machine ispreferably a horizontal forming machine. The second forming machine ispreferably a rotary drum forming machine, preferably located above thefirst forming machine.

It will be understood moreover that by the use of appropriate feedstations, it is possible to manufacture multi-compartment pouchesincorporating a number of different or distinctive compositions and/ordifferent or distinctive liquid, gel or paste compositions.

Detergent Composition of the Unit Dose Product

At least one of the compartments of the unit dose product comprises themain wash detergent composition. One embodiment of the Unit Dose ProductDetergent is shown below.

Unit Dose composition Wt % Glycerol (min 99) 5.3 1,2-propanediol 10.0Citric Acid 0.5 Monoethanolamine 10.0 Caustic soda — Dequest 2010 1.1Potassium sulfite 0.2 Nonionic Marlipal C24EO7 20.1 HLAS 24.6 Opticalbrightener FWA49 0.2 Polyorganosiloxane Fluid-Silicone Resin Mixture¹0.05-15 C12-15 Fatty acid 16.4 Polymer Lutensit Z96 2.9Polyethyleneimine ethoxylate PEI600 E20 1.1 MgC12 0.2 Enzymes ppm¹Polyorganosiloxane Fluid-Silicone Resin Mixture of Example 1

Processes of Making Cleaning Compositions

The cleaning compositions, such as, but not limited to, the fabric carecompositions of the present disclosure can be formulated into anysuitable form and prepared by any process chosen by the formulator,non-limiting examples of which are described in U.S. Pat. Nos.5,879,584; 5,691,297; 5,574,005; 5,569,645; 5,565,422; 5,516,448;5,489,392; and 5,486,303.

Methods of Using Fabric Care Compositions

The fabric care compositions disclosed in the present specification maybe used to clean or treat a fabric, such as those described herein.Typically at least a portion of the fabric is contacted with anembodiment of the aforementioned fabric care compositions, in neat formor diluted in a liquor, for example, a wash liquor and then the fabricmay be optionally washed and/or rinsed. In one aspect, a fabric isoptionally washed and/or rinsed, contacted with an embodiment of theaforementioned fabric care compositions and then optionally washedand/or rinsed. For purposes of the present disclosure, washing includesbut is not limited to, scrubbing, and mechanical agitation. The fabricmay comprise most any fabric capable of being laundered or treated.

The fabric care compositions disclosed in the present specification canbe used to form aqueous washing solutions for use in the laundering offabrics. Generally, an effective amount of such compositions is added towater, preferably in a conventional fabric laundering automatic washingmachine, to form such aqueous laundering solutions. The aqueous washingsolution so formed is then contacted, preferably under agitation, withthe fabrics to be laundered therewith. An effective amount of the fabriccare composition, such as the liquid detergent compositions disclosed inthe present specification, may be added to water to form aqueouslaundering solutions that may comprise from about 500 to about 7,000 ppmor even from about 1,000 to about 3,000 pm of fabric care composition.

In one aspect, the fabric care compositions may be employed as a laundryadditive, a pre-treatment composition and/or a post-treatmentcomposition.

While various specific embodiments have been described in detail herein,the present disclosure is intended to cover various differentcombinations of the disclosed embodiments and is not limited to thosespecific embodiments described herein. The various embodiments of thepresent disclosure may be better understood when read in conjunctionwith the following representative examples. The following representativeexamples are included for purposes of illustration and not limitation.

Test Methods Time-to Wick (T2W) Measurement Protocol

The fabric Time to Wick property is measured as follows: The test isconducted in a room or chamber with air temperature of 20-25° C. andRelative Humidity of 50-60%. All fabrics and paper products used in thetest are equilibrated in the temperature and humidity condition of thetest location for 24 hrs prior to collecting measurements. On a flat,horizontal and level, impermeable surface, place 1 piece of test fabric8 cm×10 cm in size, on top of a single sheet of kitchen paper towel (egBounty). The fabric surface facing upwards, which is not in contact withthe paper towel, can be either side of the fabric. Visually confirm thatthe fabric is lying flat and in uniform contact with the paper towelbefore proceeding. Distilled Water is used as the testing liquid.Automated single or multi-channel pipettes (eg Rainin, Gilson,Eppendorf), are used to deliver a liquid droplet size of 300 μL of thetesting liquid onto the fabric surface. A stop-watch or timer is used tocount time in seconds, from the moment when the liquid droplet contactsthe fabric surface. The timer is stopped when the whole droplet of thetest liquid wets into the fabric. The point when the liquid droplet wetsinto the fabric is determined by visual observation that the liquiddroplet has moved from sitting above the fabric surface to havingcompletely penetrated into the fabric. The time period shown elapsed onthe timer is the Time to Wick Measurement. The test is stopped after 20minutes if wetting of the liquid droplet has not been seen yet. The Timeto Wick measurement is recorded as >20 mins in this case. If wetting ofthe liquid is seen immediately upon contact of the droplet with thefabric surface, then the Time to Wick property is recorded as 0 for thatfabric. Multiple repeats are performed for each test fabric. Thesereplicates are comprised of 10 pieces of each test fabric, and 3droplets of test liquid per piece of fabric, resulting in a total of 30droplets being measured per test fabric. In addition to the average ofthe 30 Time to Wick measurements, the Standard Deviation and the 95%confidence interval should also be reported.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A surface treatment composition which comprises:A.) a polyorganosiloxane-silicone resin mixture comprising: i.) fromabout 50% to about 99.99% by weight of one or more polyorganosiloxanefluid compounds, wherein each polyorganosiloxane fluid compound containsat least about 80 mol % of units selected from the group consisting ofunits of the general formulae Ia, Ib, II and III:R¹ ₂SiO_((2/2))  (Ia),R¹ _(a)R² _(b)SiO_((2/2))  (Ib),R³ ₃SiO_((1/2))  (II),R³ ₂R⁴SiO_((1/2))  (III), in which: a has the value 0, 1 or 2, b has thevalue 1 or 2, and the sum of a and b is equal to 2; R¹ means monovalenthydrocarbon residues with 1 to 40 carbon atoms, optionally substitutedwith halogens; R² means either: a) aminoalkyl residues of the generalformula IV:—R⁵—NR⁶R⁷  (IV), wherein: R⁵ means divalent hydrocarbon residues with 1to 40 carbon atoms, R⁶ means monovalent hydrocarbon residues with 1 to40 carbon atoms, H, hydroxymethyl or alkanoyl residues, and R⁷ means aresidue of the general formula V—(R⁸—NR⁶)_(x)R⁶  (V),  wherein:  x has the value 0 or an integer valuefrom 1 to 40, and  R⁸ means a divalent residue of the general formula VI—(CR⁹ ₂—)_(y)—  (VI),  wherein:  y has an integer value from 1 to 6, and R⁹ means H or monovalent hydrocarbon residues with 1 to 40 carbonatoms, or b) aminoalkyl residues of the general formula IV wherein R⁶and R⁷ together with the N atom forms a cyclic organic residue with 3 to8 —CH₂— units, and where nonadjacent —CH₂— units can be replaced byunits that are chosen from —C(═O)—, —NH—, —O—, and —S—, R³ meansmonovalent hydrocarbon residues with 1 to 40 carbon atoms optionallysubstituted with halogens, R⁴ means the residues —OR or —OH, wherein Rmeans monovalent hydrocarbon residues with 1 to 40 carbon atoms,optionally substituted with halogens, wherein: the average ratio of thesum of units of formulae Ia and Ib to the sum of units of formulae IIand III within the one or more polyorganosiloxane fluid compounds rangesfrom about 0.5 to about 500, the average ratio of units of formula II tothe units of formula III within the one or more polyorganosiloxane fluidcompounds ranges from about 1.86 to about 100, and the one or morepolyorganosiloxane fluid compound have an average amine number of atleast about 0.01 meq/g of polyorganosiloxane fluid compounds; ii.) atleast about 0.01% by weight of one or more silicone resins, each ofwhich contain at least about 80 mol % of units selected from the groupconsisting of units of the general formulas VII, VIII, IX and XR¹⁰ ₃SiO_(1/2)  (VII),R¹⁰ ₂SiO_(2/2)  (VIII),R¹⁰SiO_(3/2)  (IX),SiO_(4/2)  (X), in which: R¹⁰ means H, —OR, —OH residues, or monovalenthydrocarbon residues with 1 to 40 carbon atoms, optionally substitutedwith halogens, and at least about 20 mol % of the units are selectedfrom the group consisting of units of the general formulas IX and X, anda maximum of about 10 wt % of the R¹⁰ residues are —OR and —OH residues;and iii) a maximum of about 5% by weight water; and B) a carrier.
 2. Asurface treatment composition according to claim 1, wherein the surfacetreatment composition is selected from the group consisting of laundryspray composition, laundry rinse additive composition, liquid laundrydetergent compositions, solid laundry detergent compositions, hardsurface cleaning compositions, liquid hand dishwashing compositions,solid automatic dishwashing compositions, liquid automatic dishwashing,tablet form automatic dishwashing compositions and laundry detergentcompositions and unit dose form automatic dishwashing compositions andlaundry detergent compositions contained in a water-soluble pouch.
 3. Asurface treatment composition according to claim 1, wherein thecomposition further comprises a perfume.
 4. A surface treatmentcomposition according to claim 1, wherein the composition furthercomprises a dye transfer inhibitor.
 5. A surface treatment compositionaccording to claim 1, further comprising a surfactant system.
 6. Asurface treatment composition according to claim 5 where the surfactantsystem comprises C₁₀-C₁₆ alkyl benzene sulfonates.
 7. A surfacetreatment composition according to claim 5, wherein the surfactantsystem comprises C₈-C₁₈ linear alkyl sulfonate surfactant.
 8. A surfacetreatment composition according to claim 6, wherein the surfactantsystem further comprises one or more co-surfactants selected from thegroup consisting of nonionic surfactants, cationic surfactants, anionicsurfactants and mixtures thereof.
 9. A surface treatment compositionaccording to claim 1, wherein the composition further comprises one ormore cleaning adjunct additives.
 10. A surface treatment implementcomprising a nonwoven substrate and the surface treatment compositionaccording to claim
 1. 11. A surface treatment composition according toclaim 1, wherein the composition comprises from about 0.001% to about95% by weight of the composition, of the polyorganosiloxane-siliconeresin mixture.
 12. A surface treatment composition according to claim 1,wherein the silicone resin of the polyorganosiloxane-silicone resinmixture is an MQ resin which contain at least about 80 mol % of unitsselected from the group consisting of unit of the formula VII and X, andthe average ratio of the units of formula VII to the units of formula Xranges from about 0.25 to about 4.0.
 13. A surface treatment compositionaccording to claim 1, wherein the polyorganosiloxane fluid compound ofthe polyorganosiloxane-silicone resin mixture contains at least about95% of units selected from the group consisting of general formulae I,II, and III.
 14. A surface treatment composition according to claim 13,wherein the monovalent hydrocarbon residues R, R¹, R³, R⁶, R⁹ and R¹⁰are alkyl residues with 1 to 6 carbon atoms or phenyl residues.
 15. Asurface treatment composition according to claim 13, wherein theresidues R² are chosen from the group consisting of —CH₂NR⁶R⁷,—(CH₂)₃NR⁶R⁷, and —(CH₂)₃N(R⁶)(CH₂)₂N(R⁶)₂.
 16. A surface treatmentcomposition according to claim 1, wherein the viscosity of the one ormore polyorganosiloxane fluid compound is from about 10 mPa·s to about10,000 mPa·s at 25° C.
 17. A surface treatment composition according toclaim 1, wherein the polyorganosiloxane-silicone resin mixture comprisesfrom about 5 to about 50 parts by weight MQ silicone resins.
 18. Asurface treatment composition according to claim 1, wherein thepolyorganosiloxane-silicone resin mixture comprises a maximum of about 2parts by weight water.
 19. A surface treatment composition according toclaim 1, wherein the polyorganosiloxane-silicone resin mixture furthercomprises a solvent which is selected from the group consisting ofmonoalcohols, polyalcohols, ethers of monoalcohols, ethers ofpolyalcohols, and mixtures thereof.
 20. A surface treatment compositionaccording to claim 1, wherein the polyorganosiloxane-silicone resinmixture has a viscosity of from about 100 to about 10,000 mPa·s at 25°C.
 20. 21. A surface treatment composition according to claim 1, whereinthe average ratio of units of formula II to the units of formulas IIIwithin the one or more polyorganosiloxane fluid compounds ranges fromabout 7 to about 99.